Crystalline Resin Sandwich Films

ABSTRACT

A resin composition that is storable at ambient temperatures. The resin composition forms a cured resin when exposed to a curing agent and heated to a curing temperature that is relatively close to ambient temperature. The resin composition includes a crystalline resin component that is sandwiched between two non-crystalline resin components to provide a zone that is rich in crystalline thermosetting resin. The crystalline thermosetting resin has a melting point that is above ambient temperature, but below the curing temperature. The viscosity of the resin component changes from a high viscosity state to a low viscosity state when the temperature is increased from ambient temperature to the curing temperature.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates generally to thermosetting resins and themany different types of compositions that contain such thermosettingresins. More particularly, the invention involves those types ofthermosetting resins and compositions that are stored at ambienttemperatures and then cured by adding a curing agent and increasing thetemperature of the resin to a curing temperature that is relativelyclose to the storage temperature. The present invention involvesproviding resins that have a relatively high viscosity at ambientstorage temperatures and are suitable for use as adhesives and inprefabricated uncured composites known as prepreg. The resins areconverted to a low viscosity material when heated to curing temperaturesto provide a rapid flow of the resin that may be required for adequatemixing with curing agents and/or penetration into porous bodies such asfiber bundles and fabric.

2. Description of Related Art

Thermosetting resins are used as a principal ingredient in a multitudeof different materials. For example thermosetting resins are widely usedalone or in combination with certain additives to form adhesives.Thermosetting resins are also combined with a wide variety of fibertypes and configurations to form composite materials. Epoxy resins,vinyl ester resins and cyanate ester resins are examples ofthermosetting resins that have been in widespread use for many years.

The curing procedure for thermosetting resins typically involves addingone or more curing agents to the uncured resin to form an activatedresin. The activated resin is then usually heated for a sufficient timeto completely cure the resin. In many situations, it is desirable toprepare the activated resin and then store it for later use. Duringstorage, the activated resins must be kept at temperatures that are wellbelow the curing temperature of the resin in order to avoid prematurecuring. For this reason, many activated thermosetting resins cannot bestored at ambient temperatures. Accordingly, it has been common in thepast to keep such activated resins refrigerated until they are ready tobe used.

Composite materials are used extensively in situations where highstrength and low weight are desired. Composites typically include fibersand a resin formulation as the two principal elements. Wide ranges offiber types, sizes and orientations have been used in composites. Glass,graphite, carbon, p-aramid, m-aramid, quartz, thermoplastic, boron,ceramic and natural fibers are common. The fibers can be chopped,stretch broken, randomly oriented, unidirectional in orientation orwoven into fabric. The fibers used in composite materials have diametersthat range from extremely small to relatively large. Although it ispossible to make composites using large diameter fibers, the more commonpractice is to take thousands of fibers having extremely small diametersand form them into individual bundles known as tows. These multi-fibertows are much stronger and more flexible than single fibers having thesame overall dimensions. Filament bundles can have a wide variety ofcross-sectional shapes including ellipsoidal, kidney and pea shapes. Thetows can be woven into fabric in the same manner as conventional yarns.Alternatively, the tows are arranged in parallel to provide aunidirectional fiber orientation or they can be randomly oriented.

Thermosetting resins have been widely used as the resin matrix incomposite materials. There are a number of ways to combine the resinwith the fibers to form the final composite. One approach that has beenused for years is to impregnate the fibers with activated resin andallow the resulting “lay-up” to cure at room temperature. The cure timeis usually reduced substantially by heating the lay-up. This type ofprocess is well suited for use in the field. However, this wet lay-upprocess has a disadvantage in that it is difficult to accurately controlthe amount of resin that is applied to the fibers and ensure that theresin is being uniformly impregnated into the fibers. In addition, theamounts of curing agent and other additives that are added to the resinmay vary between lay-ups.

In order to avoid the above problems, it has been common practice toform prefabricated lay-ups that include fibers, resin and curing agent.These prepregs are made under manufacturing conditions that allow theamount and distribution of resin and curing agent within the fibers tobe carefully controlled. The prepregs are typically refrigerated duringstorage and shipping to prevent premature curing of the resin matrix.The need to refrigerate prepreg presents a number of problems. It isexpensive to store and ship prepreg on a commercial level because largerefrigeration units are required and refrigerated trucks must be used.In addition, the temperature of the prepreg must be continuallymonitored to detect any increase in temperature due to equipment failureor the like. Increases in temperature, even for short periods of time,can adversely affect the shelf life and function of the prepreg andresult in the prepreg being discarded.

One approach to eliminating the need for refrigeration of prepreginvolves placing the resin and curing agent in the prepreg structure sothat they are physically separated from each other. For example, theresin and curing agent can be located on opposite sides of a layer ofwoven fabric to form a prepreg that can be stored indefinitely at roomtemperature as described in U.S. patent application Ser. No. 10/648,159.When ready for use, the prepreg is heated, usually under pressure, sothat the resin and curing agent flow into the fabric to initiate thecuring process. The basic approach used in these types of systems is tostore the resins and curing agents as separate entities that are insufficiently close proximity to each other so that they can be mixedtogether by heating. This type of approach can also be used forthermosetting adhesives and other applications where the structure ofthe system allows the resins and curing agents to be kept in closeproximity to each other without contact. Such systems typically includea porous body of some type that provides the structure in which theresin and curing agents are located.

There are a number of desirable properties that the resins and curingagents should have in order to be used in the ambient temperaturestorage systems described above. For example, the resin should besufficiently viscous at room temperature so that it does not flow to anyappreciable extent into contact with the curing agent. At the same time,the resin must retain sufficient tackiness and other properties that aredesirable in a prepreg. The resin should be convertible to a relativelylow viscosity material when heated to provide rapid and thorough mixingof the resin and curing agent. For resins that cure at relatively lowtemperatures, the change in resin viscosity should occur at temperaturesthat are relatively close to room temperature. For example, theviscosity change should preferably occur within 10° C. to 60° C. aboveambient temperatures.

There is a present and continuing need to develop resins that aresuitable for use in prepreg and other systems of the type describedabove that can be stored at ambient temperatures. In addition, there isa present and continuing need to develop prepreg and other systemconfigurations that include resin/curing agent combinations that can bestored at ambient temperatures while still demonstrating the ability toundergo efficient cure at temperatures not significantly higher thanambient temperature. Cure temperatures below 100° C., more preferablybelow 80° C., and most preferably as low as 60° C. are of increasinginterest to resin and/or prepreg converters because the use of thesetemperatures offers significant benefits in terms of energy consumption.Furthermore, as the cure temperature is decreased the processingequipment needed to cure the epoxy resin formulations becomes somewhatsimpler and less expensive. For example, it becomes possible to usetemporary, bespoke curing ovens constructed using inexpensive,relatively temperature-sensitive components such as wood andpolyolefinic sheeting. The resins should undergo relatively largereductions in viscosity over relatively small increases in temperatureto provide thorough mixing of the resin and curing agent as well asuniform distribution of the resin throughout the cured structure.

One approach for providing such room temperature stabile prepregs hasinvolved the use of gelator-stabilized resin compositions that aredescribed in PCT Application No. IB2004/000944. The resins include aliquid part that is composed of one or more non-crystallinethermosetting resins and a solid part that is composed of particles ofone or more crystalline thermosetting resins wherein the solid part isdispersed within the liquid part. The particles have a melting pointthat is above ambient temperature and below the curing temperature. Theliquid part further includes a gelation agent that is present in asufficient amount to form the liquid part into a gel that issufficiently gelatinous to maintain the particles in suspension withinthe liquid part at ambient temperature. The gelation agent has a meltingtemperature that is below the curing temperature such that the viscosityof the resin changes from a high viscosity state to a low viscositystate when the temperature of said resin composition is increased fromambient temperature to the curing temperature. This decrease inviscosity is enabled not only by the thermal breakdown of the gelationagent, but also by fusion of the crystalline resin particles. Unlikehigher molecular mass (substantially amorphous) epoxy resins, the melttransition of crystalline resins occurs over a narrow, predictable, andwell-defined temperature range.

The resins described in PCT Application No. IB2004/000944 are wellsuited for use in prepreg and other systems of the type described abovethat are designed to be stored at ambient temperatures. They areespecially useful because a relatively small increase above ambienttemperature is all that is required to convert the resin composition(liquid resin/solid resin/gelator) from a relatively viscous and tackymaterial to a flowing material that can penetrate porous structures,such as fiber bundles and fabric that contains fiber bundles. Uponpenetration, the resin composition mixes with the desired curing agentto provide for relatively low temperature curing of the resin.

SUMMARY OF THE INVENTION

In accordance with the present invention, uncured resin compositions areprovided that have properties similar to the gelator-stabilized resinsdescribed above, but which do not require the use of a gelation agent.The resin compositions of the present inventions have a similarviscosity profile wherein a substantial drop in viscosity occurs whenthe resin composition is heated above ambient temperatures. The presentresin compositions also have similar tack and stability at ambienttemperatures.

The present invention is based on providing a resin composition that hasa zone which is rich in crystalline thermosetting resin. The resincomposition is storable at ambient temperatures and is capable offorming a cured resin when exposed to a curing agent and heated to acuring temperature that is relatively close to ambient temperature. Theresin composition includes at least two non-crystalline components thatare composed of one or more non-crystalline thermosetting resins. Acrystalline component that includes one or more crystallinethermosetting resins is located between the two non-crystallinecomponents to provide a zone that is rich in crystalline thermosettingresin. The crystalline thermosetting resin(s) has a melting point thatis above ambient temperature and below said curing temperature.

The resin composition may be used in the same manner as the previouslydescribed gelator-stabilized resins to form prepreg and other uncuredresin composites that include a porous body and a curing componentwherein the curing component is located separate from, but in closeproximity to the uncured resin. Upon heating above ambient temperature,the resin composition is converted into a low viscosity material thatpenetrates relatively rapidly into the porous structure and mixesthoroughly with the curing component. As an additional feature of thepresent invention, fabric and other porous bodies may be located in thecrystalline component and/or the non-crystalline component of the resincomposition.

The above described and many other features and attendant advantages ofthe present invention will become better understood by reference to thefollowing detailed description when taken in conjunction with theaccompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a diagrammatic representation of an exemplary embodiment ofthe present invention where the crystalline component is shown as a filmor particles located between two layers of non-crystalline component.

FIG. 2 is a diagrammatic representation of an exemplary method formaking a resin composition in accordance with the present invention.

FIG. 3 is a diagrammatic representation of a prepreg in which the porousbody is woven fabric that has been impregnated with a curativecomponent. The uncured resin is provided in accordance with the presentinvention as a resin composition that is located on either side of thefabric.

FIGS. 4A-4D are diagrammatic representations of four exemplary prepregconfigurations in accordance with the present invention.

FIG. 5A-5C are diagrammatic representations of three exemplary prepregconfigurations in accordance with the present invention. FIG. 5D is adiagrammatic representation of an adhesive in accordance with thepresent invention wherein the curative agent and the resin compositionare separated by a fusible barrier.

DETAILED DESCRIPTION OF THE INVENTION

Resin compositions in accordance with the present invention are intendedfor use in situations where the uncured resin is stored at ambient orroom temperature over extended periods of time. For the purposes of thisspecification, “ambient” or “room” temperature is considered to betemperatures between about 10° C. and about 30° C. More preferably,ambient or room temperature is between about 20° C. and 25° C. Theuncured resin compositions form a cured resin when exposed to a curingagent and heated to a curing temperature that is higher than the ambienttemperature at which the uncured resin is stored. The difference betweenthe ambient storage temperature and the curing temperature rangesbetween 10° C. and 60° C. Curing temperatures of 40° C.-90° C. arepreferred. The resin compositions are in a high viscosity state when theuncured resin is at ambient temperatures. The viscosity of the uncuredresin in the high viscosity state is such that the resin does not flowfreely, but still retains a certain degree of tackiness that is requiredin many applications. The viscosity of the uncured resin composition inthe high viscosity state will vary between the portions or zones thatare rich in the crystalline thermosetting resin and the portions orzones that are composed entirely of non-crystalline resin. For thoseportions or layers that are composed mainly of non-crystalline resin, itis preferred that the viscosity of the uncured resin in the highviscosity state be between about 20 Pas and 70 Pas at 60° C.

In the high viscosity state, the uncured resin can be stored inrelatively close proximity to curative components that contain one ormore curing agents. When the temperature of the resin composition isincreased from ambient temperature to the curing temperature, theuncured resin is converted to a low viscosity state. The uncured resinis substantially more viscous in the high viscosity state than in thelow viscosity state The uncured resin in the low viscosity state is ableto flow relatively freely into contact with the curative component. Theviscosity of the uncured resin in the low viscosity state is preferablybetween about 10 Pas and 0.1 Pas at the desired curing temperature. Thecrystalline resin melts and mixes with the non-crystalline resin duringconversion of the uncured resin to the low viscosity state. Thisprovides a uniform resin composition having a uniform viscosity. This isin contrast to the high viscosity state where the viscosity variesbetween the crystalline and non-crystalline components.

The uncured resin is in the form of a sandwich structure wherein acrystalline resin component is located between layers of non-crystallineto provide a zone that is rich in crystalline thermosetting resin. Thenon-crystalline layers or components contain one or more non-crystallinethermosetting resins. The crystalline resin component includes one ormore crystalline thermosetting resins. The non-crystalline thermosettingresins may be any of the resins that can be stored at ambienttemperatures and that can be cured with appropriate curing agents at thecuring temperatures set forth above. Resins that are suitable includeepoxy resins, vinyl esters, unsaturated polyesters, isocyanates,phenolics and cyanate esters. Exemplary resins include epoxy resins suchas the glycidyl derivatives of bisphenol A and bisphenol F; the glycidylderivatives of p-aminophenol and m-aminophenol; monoglycidyl derivativesof aromatic, aliphatic and alicyclic alcohols such as cresyl glycidylether, t-butylphenyl glycidyl ester of neodecanoic acid; polyglycidylderivatives of polyhydroxy compounds such as glycerol,trimethylolpropane and butanediol; 3,4-epoxycyclohexylmethyl3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide, hydrogenatedbisphenol A diglycidyl ether, bis(2,3-epoxycyclopentyl)ether, thediglycidyl ester of 1,2-cyclohexanedicarboxylic acid, diglycidylphthalate; aliphatic amines such as 1,3-propanediamine, N,N-diethyl1,3-propanediamine, triethylene tetramine, diethylene triamine,4,7,10-trioxadecane-1,13-diamine, m-xylylene diamine; aromatic aminessuch as benzyldimethylamine, benzylamine, 2-4-diethyl toluene diamineand its mixtures, 2,4-dithiomethyl toluenediamine,tris(dimethylaminomethyl)phenol; alicyclic and heterocyclic amines suchas 1,3-cyclohexane diamine, 1,2-cyclohexane diamine, isophorone diamine,p-menthane diamine, methylenebis-(4-cyclohexylamine) and its alkylsubstituted derivatives, 1,3-bis-(aminomethyl)cyclohexylamine,aminoethyl piperazine, bis(aminopropyl)-piperazine, 1-methylimidazoleand other imidazoles; anhydrides such as hexahydrophthalic anhydride,methylhexahydrophthalic anhydride, methyl nadic anhydride; cyanateesters such as the dicyanate esters of bisphenol E, bisphenol A,bisphenol F; vinyl esters such as the acrylate and methacrylate estersof bisphenol A diglycidyl ether and their substituted derivatives andtheir mixtures with monomeric diluents such as styrene, methacrylatesand acrylates; diluents and flexibilizers of many classes well known inthe art; flame retardants such as those containing phosphorous,including phosphates and phosphonates; catalysts such as borontrihalides and their amine adducts and mixtures thereof with diluentsand carriers; peroxides and hydroperoxides.

The crystalline component of the resin composition that is located orsandwiched between the non-crystalline resin component is preferably inthe form of one or more films or crystalline resin particles thatprovide a zone which is rich in crystalline thermosetting resin. Theterm “rich” is intended to include crystalline thermosetting resinconcentrations that range from 50 weight percent up to 100 weightpercent. For example, a crystalline resin film that is composed entirelyof crystalline thermosetting resin provides a well-defined zone that isrich (for example, 99+ weight percent) in crystalline thermosettingresin. When particles of crystalline resin are used, the zone that isrich in crystalline thermosetting resin will typically have less than100 weight percent crystalline resin. The actual concentration will varydepending upon the amount and size of crystalline resin particles andthe amount of non-crystalline resin that has infused into the particlespresent in crystalline-rich zone. Particle sizes that range from 10 mmdown to 0.001 mm are suitable. Particles that are smaller than 2 mm arepreferred with particle sizes of between 0.5 mm and 0.15 mm beingparticularly preferred. The particles can be made from any thermosettingpolymer or resin that is crystalline at room temperature and has amelting point that is below the curing temperature selected for theparticular resin composition. Exemplary preferred crystalline resinparticles are made from materials such as, crystallized Ruetapox 0158that is available from Bakelite AG (Duisberg, Germany) and crystallizedDER 332 that is available from Dow Chemical Company (Wilmington, Del.).As mentioned above, the crystalline resin may also be in the form of oneor more films instead of particles wherein the films are made from thesame materials as the particles using known film forming processes.

The amount of crystalline resin that is located between thenon-crystalline layers may be varied. It is preferred that the amount ofcrystalline resin be sufficient to provide the desired drop in viscositywhen the resin composition is heated above ambient temperature and thecrystalline resin melts and mixes with the non-crystalline layers. Theactual amount of crystalline resin needed to achieve the target high andlow viscosity states can be determined by routine experimentation.Typically, from 0.5 to 10 parts by weight per square meter ofcrystalline resin will be sandwiched between 1 part by weight per squaremeter of total non-crystalline resin located on both sides of thecrystalline resin. A preferred loading is 1 part crystalline resin persquare meter sandwiched between 1 part total liquid resin per squaremeter. An example of a typical sandwich film will contain about 200grams per square meter (gsm) of crystalline resin sandwiched between twolayers of non-crystalline resin that contain about 100 gsm resin each.

The uncured resin compositions are preferably prepared by applying thecrystalline resin to the surface of a layer of non-crystalline resin andthen applying a second layer of non-crystalline resin to form acrystalline resin sandwich or composition as shown in FIG. 1 at 10. Thecrystalline resin sandwich or composition 10 includes a crystallineresin component that is shown as particle layer or zone 12 and anon-crystalline resin component that is made up of layers or films ofnon-crystalline resin 14 and 16. The two non-crystalline layers 14 and16 may be composed of the same or different resins. The crystallineparticle layer 12 can be formed by sprinkling particles of crystallineresin onto the surface of layer 14. The particles may be compacted intothe resin layer 14, if desired. Alternatively, the crystalline resin canbe formed into a resin film that is sandwiched between the twonon-crystalline layers 14 and 16. Either way, a zone 12 is provided inthe center of the composition that is rich in crystalline thermosettingresin. If desired, reinforcing fibers or fabric may be located in eitherthe crystalline component or the non-crystalline component. The outerresin layers 14 and 16 consolidate with the crystalline layer 12 toprovide a dispersion of crystalline resin with liquid (non-crystalline)resin such that the outer layers are substantially of the correct aspectand viscosity for use in composite manufacturing processes and thecrystalline resin is substantially hosted completely within thenon-crystalline resin layers.

The resin composition is preferably in the form of a sandwich film thatcan be stored “as is” or combined with a curative component prior tostorage or use. Configurations other than thin films are possibledepending upon the final intended use of the resin composition. Atambient temperature, the outer layers containing the non-crystallineresin are in a relatively high viscosity state and can be stored forrelatively long storage times. Storage times may be as short as a fewhours or as long as a few months or more.

The uncured crystalline resin sandwich is preferably stored incombination with a curative component that is located in close proximityto the resin, but not in chemical contact therewith. The crystallineresin sandwich and curative component may simply be stored side by sidewith a barrier located between them. However, it is preferred that thecrystalline resin sandwich and curative component be stored incombination with one or more porous bodies that provide a structure inwhich the crystalline resin sandwich and curative component may bestored in close proximity without chemical contact. The porous body canbe anything that has an exterior surface and interior surfaces that arelocated within the porous body. The preferred porous bodies are thosecomposed of the fibers that are used in making composite materials.Other porous bodies that may be used include open cell foam, honeycomband thermoplastic scrims.

If desired, an optional removable reaction barrier may be provided tokeep the crystalline resin sandwich from prematurely contacting any ofthe curative component. The removable barrier is preferably made from athin polymeric film that melts or otherwise is dissolved by the resin attemperatures between the ambient temperature at which the composition isstored and the curing temperature. Examples of suitable barrier filmmaterials include aqueous film-forming emulsions and dispersions ofpolyethylene; oxidized polyethylene; ethylene copolymers with acrylicand methacrylic esters and acids; polyethylene waxes; carnauba wax andother naturally derived waxes. Thin films of polyethylene,poly(ethylene-co-propylene) and other ethylene copolymers; eitherapplied as hot melts or from solution can also be used.

The curative component that is eventually combined with the crystallineresin composition includes one or more curing agents that may or may notbe dissolved or otherwise suspended in a carrier. The curing agent(s)are selected such that they provide curing of the crystalline resinsandwich when combined therewith at temperatures equal to or below theabove stated curing temperatures. The amount of curing agent required toprovide adequate curing of the resin component will vary depending upona number of factors including the type of resin being cured, the desiredcuring temperature and curing time. Curing agents typically includecyanoguanidine, aromatic and aliphatic amines, acid anhydrides, LewisAcids, substituted ureas, imidazoles and hydrazines. The particularamount of curing agent required for each particular situation may bedetermined by well-established routine experimentation. Exemplarypreferred curing agents include imidazole(1,3-diaza-2,4-cyclopentadiene) available from Sigma Aldrich (St. Louis,Mo.) 2-ethyl-4-methylimidazole available from Sigma Aldrich and borontrifluoride amine complexes, such as Anchor 1170, available from AirProducts & Chemicals, Inc. (Allentown, Pa.).

The curing component, if desired, may include a carrier for the curingagent. The curing agents are suspended or dissolved in the carrier withthe resulting mixture applied to the porous body or other surface wheremixing with the resins contained in the crystalline resin sandwich willeventually take place. Exemplary carriers include ketones, such asacetone or methylethylketone or low molecular weight polyethyleneglycol.The amount of curing agent added to the carrier and the carrier typewill vary depending upon where the curing agent is to be located and thephysical form of the curative once deposited. When the curing agent isto be located in a porous body, such as fabric, the carrier must besufficiently liquid to penetrate into the fabric. In situations wherethe curing component is in the form of a film, the carrier must besufficiently viscous to form such films. The carrier can remainassociated with the curative, for example in the case of BF3 complexeshosted in polyethyleneglycol, the curative formulation being designedsuch that the presence of the carrier does not interfere negatively withthe cured performance of the assembly. Alternatively, the carrier cansimply be used as a method for impregnation of the curative on thefabric where the carrier would typically be a higher volatility solventsuch as the aforementioned methylethylketone or acetone, that is removedin a subsequent processing step leaving the reactive curative isolatedon the porous body. Particularly exemplary of this mode of operation isthe deposition of reactive solid imidazole curatives on porous bodiesfrom acetone.

FIG. 2 is a diagrammatic representation of a prepreg 30 in which fibertows 32 are woven into a fabric 34. Crystalline resin sandwich layers ofthe type shown in FIG. 1 are located on both sides of the fabric 34 asshown at 36 and 38. The woven fabric 34 may be viewed as a compoundporous body that has discontinuous outer surfaces on either side of thefabric and interstitial spaces 42. In addition, each of the fiber tows32 forms a porous body. Accordingly, there are porous bodies (tows)located within the porous body (fabric). The curative component in thisembodiment is located within the porous structure of the individual towsas indicated by the plus symbols (+).

The present invention is especially well suited for use in prepregbecause the large reduction in viscosity that occurs when the prepreg isheated to above ambient temperature provides relatively complete andrapid penetration of both the overall fabric and the individual tows.Since the curing agents (+'s) are located in the tows, it is necessarythat the resin completely penetrate into the tows to provide uniformcuring. The tows 32 in FIG. 2 are shown having optional removablebarriers 44 surrounding each tow. It should be noted that a singlefabric layer 34 is shown sandwiched between two crystalline resinsandwich layers 36 and 38. In alternative embodiments, multiple fabriclayers can be used where not all of the layers include the curativecomponent. For example, the fabric layer 34 can be sandwiched betweentwo additional fabric layers that do not include a curative component.The crystalline resin sandwich layers on the outside of the structure,when heated, are converted to relatively low viscosity resins that areable penetrate through the additional layers before contacting thecurative component. Also, as mentioned previously, the fabric layers(without curative agent) may be located within either or both of thecrystalline or non-crystalline layers of the crystalline resin sandwich.

Another exemplary prepreg is shown generally at 50 in FIG. 3. Thisprepreg is similar to the prepreg shown in FIG. 2 in that it includesfiber tows 52 that have been woven into a single layer of fabric 54 thatis sandwiched between two crystalline resin sandwich layers 56 and 58.The prepreg is shown at ambient temperature. At this temperature thecrystalline resin sandwich layers 56 and 58 are in a high viscositystate that is sufficient to prevent a substantial amount of resin fromflowing into or out of the interstitial spaces 60 and/or away from theexterior surfaces of the fabric 54. In this embodiment, the curativecomponent (+'s) is located within the interstitial spaces of the fabricand not limited to the interstitial spaces of the tows. Optionalremovable reaction barriers are shown at 62 and 64. The removablereaction barrier is preferable in situations where it is desirable toeliminate any possible contact between the uncured resin and curingagent that might occur at the interface between the two components.

Four exemplary embodiments of prepreg made using the crystalline resinsandwich films of the present invention are shown in FIG. 4. The prepreg410 shown in FIG. 4A has a resin component 412 in the form of acrystalline resin sandwich layer of the type shown in FIG. 1, a curativecomponent in the form of curing agent layer 414 and a porous body in theform of dry fabric layer 416. During storage at ambient temperature, thecrystalline resin sandwich remains in a high viscosity state and doesnot flow to any substantial degree into the fabric layer 416. Inaccordance with the present invention, when the prepreg 410 is heatedunder pressure to curing temperature, the crystalline resin sandwich 412is converted to the low viscosity state and flows through the fabriclayer 416 and into contact with the curative component 414.

The prepreg shown at 420 in FIG. 4B is similar to the prepreg 410 exceptthat it includes two fabric layers 426 and 428 as well as thecrystalline resin sandwich layer 422 and curing agent layer 424. Inaccordance with the present invention, the crystalline resin sandwichlayer in the low viscosity state is sufficiently fluid that is mixesthoroughly with the curing agent and also penetrates both fabric layers.Another prepreg configuration is shown at 430 in FIG. 4C. The prepreg430 includes crystalline resin sandwich layer 432 and curing agent layer434 that are separated by and sandwiched between fabric layers 436, 438and 439. The crystalline resin sandwich becomes sufficiently fluid inthe low viscosity state to flow throughout the structure to provideuniform mixing of resin and curing agent as well as uniform penetrationof all three fabric layers. Prepreg 440 shown in FIG. 4D includescrystalline resin sandwich layer 442, curing agent layer 444 and fabriclayers 446 and 448. The prepregs shown in FIG. 4 are all similar in thatboth the crystalline resin sandwich component and curative component arein the form of thin films that are separated from each other by at leastone layer of fabric.

Three more embodiments of prepreg in accordance with the presentinvention are shown diagrammatically in FIGS. 5A-5C. Prepreg 510 (FIG.5A) includes a crystalline resin sandwich layer 512 that includes afabric layer (represented by x's) that is located in one or both of thenon-crystallized resin layers in the crystallized resin sandwich layer.The overall assembly of 510 contains a typical amount of resin which isaround 35% by weight. The curative component 514 is in the form of alayer of fabric that has been impregnated with the curing agent. Thefabric/crystalline resin sandwich layer 512 is separated from the layerof curing agent impregnated fabric 514 by a dry layer of fabric 518. Anadditional layer of dry fabric 516 may optionally be added to theprepreg, if desired. Such fabric that has been impregnated with curingagent is disclosed in French Patent application No. 0210769 andco-pending U.S. patent application Ser. No. 10/648,159. The contents ofthese applications are also specifically incorporated by reference.

In FIG. 5B, a prepreg 520 is shown where the resin component is in theform of crystalline resin sandwich film 522 that is separated from“hardenerpreg” layer 524 by a removable reaction barrier film 526.“Hardenerpreg” is a term of art used to describe fiber or other types ofreinforcement material that has the curative dispersed in, and/or on thereinforcement and wherein the reinforcement is free of resin. Theprepreg 530 in FIG. 5C includes a crystalline resin sandwich layer 532that contains an embedded fabric 532 and a hardenerpreg layer 534. Thehardenerpreg 534 and crystalline resin sandwich layer 532 are separatedby a removable reaction barrier film 536. An additional dry fabric layer538 may be placed on top of the crystalline resin sandwich layer 532, ifdesired.

An uncured resin composition in accordance with the present invention isshown at 540 in FIG. 5D. The resin composition is intended for use as anadhesive or in other situations where the uncured resin is not stored aspart of a prepreg or other porous body. The composition 540 includes acrystalline resin sandwich layer 542 and a curing agent layer 544. Aremovable reaction barrier 546 is used to separate two layers 542 and544 from each other

Examples of practice are as follows:

EXAMPLE 1

In this example, a resin composition as shown in FIG. 1 was preparedwhere a crystalline resin layer is sandwiched between twonon-crystalline resin layers. The thermosetting resin formulation usedto make the non-crystalline component was prepared by combining 16.5weight % Araldite LY 1556 resin available from Huntsman (Salt Lake City,Utah) with 40.5 weight % DER 337 resin available form Dow ChemicalCompany (Wilmington, Del.) and 43.0 weight % Araldite GT6071 alsoavailable from Huntsman. The three non-crystalline thermosetting resinswhere mixed together at 120° C. until homogeneous and then cooled toambient temperature. The resulting non-crystalline resin formulation wascast into a film with a nominal areal weight of 100 gsm.

A crystalline resin layer was formed by coating Ruetapox 0158 onto apiece of the non-crystalline film. Ruetapox 0158 is a crystalline resinthat is available from Bakelite AG (Duisberg, Germany). The Ruetapox0158 coating had a nominal areal weight of 200 gsm. A second piece ofnon-crystalline resin film was then place on top of the Ruetapox 0158coating to form a resincomposition. This composition was placed in apress at 25° C. and consolidated to form the final crystalline resincomposition that contained equal amount of crystalline andnon-crystalline resin having a total combined nominal areal weight of400 gsmPas. The viscosity of the non-crystalline resin formulation(which is the effective viscosity of the outer portions of the sandwich)is 35684 mPas at 60° C. and at 80° C. decreases to 3616 mPas. Whenheated to 60° C., the viscosity of the entire resin composition droppedto 901 mPas.

A second resin composition was prepared in the same manner as describedabove except that two layers of non-crystalline resin were located oneither side of the crystalline layer to provide a total nominal arealweight of 600 gsm and a weight ratio of non-crystalline resin tocrystalline resin per square meter of 2 to 1. The viscosity dropped to2586 mPas when the resin composition was heated to 60° C. Accordingly,the amounts of crystalline and non crystalline resin can be tailored togive the most desirable or required viscosity at the cure temperature.

EXAMPLE 2

Resin compositions were made in the same manner as EXAMPLE 1 except thatthe formulation for the non-crystalline resin component was changed to:

Araldite LY1556 13.39% by weight DER 337 35.71% by weight Epikote 100150.89% by weight ORASOL Red G 00.01% by weight

The resins were also mixed together at 120° C. until homogeneous andthen cooled to ambient temperature. Epikote 1001 is available fromResolution Performance Products (Houston, Tex.) and ORASOL Red G isavailable from Huntsman.

The viscosity of the non-crystalline resin component was 50830 mPas at60° C. When heated to 60° C., the viscosity of the entire resincomposition dropped to 1718 mPas.

EXAMPLE 3

Resin compositions were made in the same manner as EXAMPLE 1 except thatthe formulation for the non-crystalline resin component was changed to:

Araldite LY1556 11.64% by weight DER 337 31.03% by weight Epikote 100148.71% by weight N-Ethyl-p-toluenesulfonamide  8.62% by weight ORASOLYelow 3R  0.01% by weight

The resins were also mixed together at 120° C. until homogeneous andthen cooled to ambient temperature. N-Ethyl-p-toluenesuylfonamide isavailable from Sigma-Aldrich Corp. (St Louis, Mo.) and ORASOL Yellow 3Ris available from Huntsman.

The viscosity of the non-crystalline resin component was 24300 mPas at60° C. When heated to 60° C., the viscosity of the entire resincomposition dropped to 689 mPas.

EXAMPLE 4

Resin compositions were made in the same manner as EXAMPLE 1 except thatthe formulation for the non-crystalline resin component was changed to:

DER 337 55% by weight Epikote 1001 45% by weight

The resins were also mixed together at 120° C. until homogeneous andthen cooled to ambient temperature.

The viscosity of the non-crystalline resin component was 52421 mPas at60° C. When heated to 60° C., the viscosity of the entire resincomposition dropped to 1677 mPas.

EXAMPLE 5

A semi-preg was formed by placing a resin composition made according toExample 4 on the surface of a sheet of a stitched bi-axial glass fabric(nominal areal weight 600 gsm). The glass fabric had been previouslyimpregnated with Anchor 1170 which is a curing agent available from AirProducts & Chemicals, Inc. (Allentown, Pa.). The nominal loading ofAnchor 170 was 40 gsm. Four plies (approximately 100 mm×150 mm) of thissemi-preg were laid up together and cured using a vacuum bag. The baggedsemi-preg was loaded into an oven at below 40° C. and ramped at 2° C.per minute to a curing temperature of 60° C. The curing temperature wasmaintained for 1 hour. The cured laminate was cooled to ambienttemperature and removed from the vacuum assembly. The cured laminateappeared well consolidated and cured uniformly. This demonstrates thatthe viscosity profile of the crystalline resin composition was suitablefor infusion and mixing prior to cure. TA 2980 (DMA) testing gave thelaminates cure T_(g) as 73° C. (Peak tan delta). A single transition wasseen over the test range of 20 to 200° C. which indicative of goodmixing of the resin and curative component prior to curing.

Having thus described exemplary embodiments of the present invention, itshould be noted by those skilled in the art that the within disclosuresare exemplary only and that various other alternatives, adaptations andmodifications may be made within the scope of the present invention.Accordingly, the present invention is not limited to the above preferredembodiments and examples, but is only limited by the following claims.

1. A resin composition that is storable at ambient temperatures, saidresin composition forming a cured resin when exposed to a curing agentand heated to a curing temperature that is higher than said ambienttemperature, said resin composition comprising: a first non-crystallinecomponent, said non-crystalline component including one or morenon-crystalline thermosetting resins; a second non-crystallinecomponent, said second non-crystalline component including one or morenon-crystalline thermosetting resins; and a crystalline component thatcomprises one or more crystalline thermosetting resins wherein saidcrystalline component is located between said first and secondnon-crystalline components to provide a zone that is rich in said one ormore crystalline thermosetting resins and wherein said one or morecrystalline thermosetting resins has a melting point that is above saidambient temperature and below said curing temperature.
 2. A resincomposition according to claim 1 wherein said crystalline componentcomprises particles of one or more crystalline thermosetting resins. 3.A resin composition according to claim 1 wherein said crystallinecomponent is in the form of a film that comprises said one or morecrystalline thermosetting resins.
 4. A resin composition according toclaim 1 wherein said first and/or second non-crystalline componentscomprise a plurality of fibers.
 5. A resin composition according toclaim 1 wherein said crystalline component comprises a plurality offibers.
 6. A resin composition according to claim 4 wherein saidcrystalline component comprises a plurality of fibers.
 7. An uncuredcomposite that is suitable for storage at ambient temperatures, saiduncured composite comprising: a) a porous body comprising an exteriorsurface and interior surfaces located within said porous body thatdefine interstitial spaces located with said porous body; b) a resincomposition located at said exterior surface of the porous body, saidresin composition forming a cured resin when exposed to a curing agentand heated to a curing temperature that is higher than said ambienttemperature, said resin composition comprising: a first non-crystallinecomponent, said non-crystalline component including one or morenon-crystalline thermosetting resins; a second non-crystallinecomponent, said non-crystalline component including one or morenon-crystalline thermosetting resins; and a crystalline component thatcomprises one or more crystalline thermosetting resins wherein saidcrystalline component is located between said first and secondnon-crystalline components to provide a zone that is rich in said one ormore crystalline thermosetting resins and wherein said one or morecrystalline thermosetting resins has a melting point that is above saidambient temperature and below said curing temperature and wherein theviscosity of said resin component changes from a high viscosity state toa low viscosity state when the temperature of said resin component isincreased from said ambient temperature to said curing temperature; andc) a curative component comprising a curing agent for said resincomposition, said curing agent being separated from said resincomposition during storage of said uncured composite at said ambienttemperatures, wherein the viscosity of said resin component in said lowviscosity state is sufficient to allow said resin component to flow intosaid interstitial spaces.
 8. An uncured composite according to claim 7wherein said curative component is located at the interior surfaces ofsaid porous body and said resin composition is located at said exteriorsurface of said porous body.
 9. An uncured composite according to claim7 wherein said porous body comprises a plurality of fibers in the formof a fabric or unidirectional tape having a first side and a second sidethat define the exterior surface of said porous body and wherein saidresin composition is located only at the first side of said fabric orunidirectional tape and said curative component is located on saidsecond side of said fabric or unidirectional tape.
 10. An uncuredcomposite according to claim 7 where said porous body comprises aplurality of fibers in the form of a fabric or unidirectional tapehaving a first side and a second side that define the exterior surfaceof said porous body and wherein said resin component is located at boththe first side and second side of said fabric or unidirectional tape andsaid curative component is located at the interior surfaces of saidfabric or unidirectional tape.
 11. An uncured composite according toclaim 7 wherein said resin component is reactive with said curativecomponent at said ambient temperature, said curative component being inthe form of a coating that covers at least a portion of the interiorand/or exterior surfaces of said porous body to provide a plurality ofcurative coating surfaces, said composition further comprising aremovable reaction barrier located between said resin component and saidcurative coating surfaces to prevent contact of said resin component andsaid curative coating surfaces during storage of said uncured resincomposition at said ambient temperature.
 12. An uncured compositeaccording to claim 7 wherein said crystalline component comprisesparticles of one or more crystalline thermosetting resins.
 13. Anuncured composite according to claim 7 wherein said crystallinecomponent is in the form of a film that comprises said one or morecrystalline thermosetting resins.
 14. An uncured composite according toclaim 7 wherein said first and/or second non-crystalline componentscomprise a plurality of fibers.
 15. An uncured composite according toclaim 7 wherein said crystalline component comprises a plurality offibers.
 16. An uncured composite according to claim 15 wherein saidcrystalline component comprises a plurality of fibers.
 17. A cured resincomposition comprising an uncured resin composition according to claim 1that has been exposed to a curing agent and heated to said curingtemperature for a sufficient time to form said cured resin composition.18. A cured composite comprising an uncured composite according to claim7 that has been heated to said curing temperature for a sufficient timeto form said cured composite.
 19. A method for forming a resincomposition that is storable at ambient temperatures, said resincomposition forming a cured resin when exposed to a curing agent andheated to a curing temperature that is higher than said ambienttemperature, said method comprising the steps of: forming a firstnon-crystalline component, said first non-crystalline componentincluding one or more non-crystalline thermosetting resins; forming asecond non-crystalline component, said second non-crystalline componentincluding one or more non-crystalline thermosetting resins; and forminga crystalline component that comprises one or more crystallinethermosetting resins and locating said crystalline component betweensaid first and second non-crystalline components to provide a zone thatis rich in said one or more crystalline thermosetting resins and whereinsaid one or more crystalline thermosetting resins has a melting pointthat is above said ambient temperature and below said curingtemperature.
 20. A method for malting a resin composition according toclaim 19 wherein said crystalline component comprises particles of oneor more crystalline thermosetting resins.
 21. A method for making aresin composition according to claim 19 wherein said crystallinecomponent is in the form of a film that comprises said one or morecrystalline thermosetting resins.
 22. A method for making a resincomposition according to claim 19 wherein said first and/or secondnon-crystalline components comprise a plurality of fibers.
 23. A methodfor making a resin composition according to claim 19 wherein saidcrystalline component comprises a plurality of fibers.
 24. A method formaking a resin composition according to claim 22 wherein saidcrystalline component comprises a plurality of fibers.
 25. A methodaccording to claim 19 that includes the additional step of combiningsaid resin composition with a porous body and a curative componentwherein said curative component is not in contact with said resincomposition to form a curable resin composition.